Self-release type release film and preparation method thereof

Abstract

The invention relates to the technical field of self-release release films, in particular to a self-release release film and a preparation method thereof.The self-release release film is prepared from, by mass, 30-60 parts of HDPE, 20-50 parts of LDPE, 10-30 parts of LLDPE, 5-20 parts of M-LDPE, 10-30 parts of CaCO3, 0.5-2 parts of a slipping agent, 0.3-1 part of an anti-adhesion agent and 1-3 parts of an antistatic agent; and release ingredients: 10 to 15 parts of perfluorooctyl ethyl acrylate and 6 to 10 parts of trifluoroethyl methacrylate. According to the invention, the actual product has low surface energy by adding the release ingredients, the release layer forms a cross-linked network structure by virtue of the arrangement of the isocyanate curing agent which plays a role of a cross-linking agent, and the cross-linked release layer has higher stability and cohesion, so that the permeation and adsorption of viscous substances can be effectively prevented; meanwhile, the heat resistance and chemical resistance of the release film are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of self-releasing release films, and particularly to a self-releasing release film and a preparation method thereof. Background Art

[0002] A release film is a film with a separating property on its surface and has wide applications in various industrial fields and daily life.

[0003] Release films are widely used in the protection of circuit boards and chips in the electronics industry, as the base paper for labels and tapes in the printing and packaging industry, and in the automotive manufacturing industry for protecting adhesives and films on components such as car seats and dashboards.

[0004] In the actual production process of release films, existing release film products are prone to problems in terms of hardness, flatness, coefficient of thermal expansion, and thickness deviation rate, resulting in a low actual yield, and the finished products are in a large roll state, which is not convenient for actual use. For this reason, we propose a self-releasing release film and a preparation method thereof. Summary of the Invention

[0005] The purpose of the present invention is to solve the drawbacks existing in the prior art, and to propose a self-releasing release film and a preparation method thereof.

[0006] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A self-releasing release film, in parts by mass, comprises the following raw materials:

[0008] Base film: 30 - 60 parts of HDPE, 20 - 50 parts of LDPE, 10 - 30 parts of LLDPE, 5 - 20 parts of M-LDPE, 10 - 30 parts of CaCO 3 1, 0.5 - 2 parts of a slip agent, 0.3 - 1 part of an anti-sticking agent, 1 - 3 parts of an antistatic agent, 0.1 - 1 part of an antioxidant;

[0009] Release formulation: 10 - 15 parts of perfluorooctylethyl acrylate, 6 - 10 parts of trifluoroethyl methacrylate, 3 - 6 parts of hydroxyl-terminated polydimethylsiloxane, 2 - 5 parts of a curing agent, 0.01 - 0.1 part of an initiator, 100 - 150 parts of a solvent.

[0010] As a preferred technical solution of the present application, the slip agent is any one of oleic acid amide, erucic acid amide, or polydimethylsiloxane.

[0011] As a preferred technical solution of the present application, the anti-sticking agent is any one of silicon dioxide, talcum powder, or polyethylene wax.

[0012] As a preferred technical solution of the present application, the antistatic agent is any one of stearyl trimethyl ammonium chloride, sodium dodecyl sulfate, and lauryl alcohol polyoxyethylene ether.

[0013] As a preferred technical solution of the present application, the antioxidant is composed of a combination of antioxidant 1010 and antioxidant 168, and the ratio of the two is 1:1 - 1:2.

[0014] As a preferred technical solution of the present application, the curing agent is an isocyanate curing agent.

[0015] As a preferred technical solution of the present application, the solvent is a mixed solvent of fluorocarbon solvent and xylene, and the volume ratio is 2:3.

[0016] A method for preparing a self-releasing release film includes the following steps:

[0017] Step S1, preparation of base film raw materials: Weigh the following raw materials by weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-adhesive agent, antistatic agent, antioxidant, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 - 15 minutes;

[0018] Step S2, preparation of release formulation solution: perfluorooctyl ethyl acrylate, trifluoroethyl methacrylate, hydroxyl-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0019] When preparing the release formulation solution;

[0020] First, add perfluorooctyl ethyl acrylate and trifluoroethyl methacrylate to the reaction kettle in proportion, and stir and mix at room temperature to obtain a fluorinated monomer mixture;

[0021] Then, slowly add hydroxyl-terminated polydimethylsiloxane to the fluorinated monomer mixture, and continue to stir to make the two fully mixed to form a single reaction system;

[0022] Polymerization reaction: Place the reaction kettle containing the above raw materials in a constant temperature water bath for heating, control the temperature at 60°C - 80°C, start the polymerization reaction, and then gradually add the initiator thereto to initiate the polymerization reaction of the fluorinated monomer and siloxane. During the polymerization reaction, continuous stirring is required, and the reaction time is 4 - 8 hours;

[0023] Cooling and discharging: After the polymerization reaction reaches the expected degree, stop heating, let the whole reaction system cool down to room temperature naturally, and take out the product. At room temperature, add the curing agent into the product to make the curing agent fully react with the hydroxyl group in the polymer to form a cross-linked structure, improve the performance of the subsequent coating, and add solvent to adjust the concentration of the polymer to prepare a fluorosilicone polymer solution as needed, so as to facilitate the subsequent coating process;

[0024] Step S3, fully mixing and stirring the release ingredient solution and the base film raw material to form a self-release release film raw material melt;

[0025] Step S4, extrusion film blowing: adding the mixed raw material melt into the barrel of the extruder, and gradually heating, melting and plasticizing the raw material through the heating of the extruder and the rotation of the screw. The temperature in this process is maintained at 150°C-250°C. The plasticized melt is extruded through the die head to form a tubular film, and then compressed air is immediately introduced into the tube to blow the tubular film into a desired diameter and thickness. At the same time, the end of the film is pulled by a pulling device to ensure continuous production. In this process, the blowing ratio is 2-3 and the pulling speed is 5-15m / min;

[0026] Step S5, preliminary cooling and shaping, the inflated film passes through an air cooling system, and by arranging multiple cooling air rings around the film, cold air is blown to the surface of the film to quickly cool the film. The temperature of the cooling air is 10°C-30°C, so that the surface temperature of the release film is initially reduced to 80°C;

[0027] Step S6, release force differentiation treatment: by arranging gas spray guns on the upper and lower sides of the pulled film, nitrogen spraying treatment is performed on the upper and lower sides of the film through the spray guns;

[0028] The spray gun pressure on the upper surface is 0.3MPa, the gas flow rate is 30L / min, and the treatment time is 30s; the spray gun pressure on the lower surface is 0.2MPa, the gas flow rate is 20L / min, and the treatment time is 20s;

[0029] Then, the film is cooled again to naturally cool to room temperature. In the above treatment process, the gas parameters are processed during the treatment process on both sides so that the surface property change on the lower side is smaller than that on the upper side, thereby adjusting the release force on both sides of the release film to meet actual needs.

[0030] Step S7, reprocessing the finished product. During the processing, the release film is trimmed by a die-cutting device, and the easy-tear line of the release film after the die-cutting and trimming is pressed by a rotary creasing machine to facilitate subsequent practical use.

[0031] The beneficial effects of the present invention are:

[0032] In the actual production process of the present invention, the component ratio in the production process of the release film can be adjusted according to actual needs, so as to adjust and control the hardness, flatness, coefficient of thermal expansion and thickness deviation rate of the finished release film, facilitating the production of a self-release release film that meets the requirements according to needs.

[0033] Moreover, in the production process, through the addition of the configured release ingredients, the actual product has a lower surface energy, and an isocyanate curing agent is added, which acts as a good cross-linking agent, enabling the release layer to form a cross-linked network structure. The cross-linked release layer has higher stability and cohesion, can effectively prevent the penetration and adsorption of sticky substances, and at the same time improves the heat resistance and chemical resistance of the release film, better enhancing the self-release performance of the product.

[0034] And in the production process, through the gas injection treatment with nitrogen inert gas and the adjustment of parameters during the injection treatment, the differential adjustment of the release force on the upper and lower surfaces of the self-release release film is achieved, realizing the differential adjustment of the upper and lower properties of the product, so as to better meet the use of the product in the actual environment and improve the actual use adaptability. Detailed implementation mode

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments.

[0036] Embodiment 1

[0037] A self-release release film comprises raw materials with the following masses:

[0038] Base film: 30 g of HDPE, 20 g of LDPE, 10 g of LLDPE, 5 g of M-LDPE, 10 g of CaCO 3 10 g, 0.3 g of slip agent, 0.3 g of anti-sticking agent, 1 g of antistatic agent, 0.3 g of antioxidant;

[0039] Release ingredients: 10 g of perfluorooctylethyl acrylate, 6 g of trifluoroethyl methacrylate, 3 g of hydroxyl-terminated polydimethylsiloxane, 2 g of curing agent, 0.01 g of initiator, 100 g of solvent.

[0040] Further, the slip agent is oleic acid amide.

[0041] Further, the anti-sticking agent is silica.

[0042] Further, the antistatic agent is stearyl trimethyl ammonium chloride.

[0043] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio, and the ratio of the two is 1:1.

[0044] Further, the curing agent is an isocyanate curing agent.

[0045] Further, the solvent is a mixed solvent of a fluorocarbon solvent and xylene, and the volume ratio is 2:3.

[0046] A method for preparing a self-releasing release film includes the following steps:

[0047] Step S1, preparation of base film raw materials: Weigh the following raw materials by weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 minutes;

[0048] Step S2, preparation of release formulation solution: Perfluorooctylethyl acrylate, trifluoroethyl methacrylate, hydroxyl-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0049] When preparing the release formulation;

[0050] First, add perfluorooctylethyl acrylate and trifluoroethyl methacrylate to the reaction kettle in proportion, and stir and mix at room temperature to obtain a fluorinated monomer mixture;

[0051] Then, slowly add hydroxyl-terminated polydimethylsiloxane to the fluorinated monomer mixture and continue stirring to make the two fully mixed to form a single reaction system;

[0052] Polymerization reaction: Place the reaction kettle containing the above raw materials in a constant temperature water bath for heating, control the temperature at 60 °C, start the polymerization reaction, and then gradually add the initiator thereto to initiate the polymerization reaction of the fluorinated monomer and the siloxane. During the polymerization reaction, continuous stirring is required, and the reaction time is 4 hours;

[0053] Cooling and discharging: After the polymerization reaction reaches the expected degree, stop heating, let the overall reaction system cool naturally to room temperature, and take out the product. At room temperature, add the curing agent to the product mixture to make the curing agent fully react with the hydroxyl groups in the polymer to form a cross-linked structure, improve the performance of the subsequent coating, and add a solvent as needed to adjust the concentration of the polymer to make a fluorosilicon polymer solution for facilitating the subsequent coating process;

[0054] Step S3, fully mix and stir the release formulation solution and the base film raw materials to form a melt of the self-releasing release film raw materials;

[0055] Step S4, Extrusion Blown Film: Add the mixed base film raw materials into the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw materials are gradually heated and melted and plasticized. The temperature during this process is maintained at 150°C. The plasticized melt is extruded through the die head to form a tubular film. Then, compressed air is immediately introduced into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the end part pulls the film through the traction device to ensure continuous production. During this process, the blow-up ratio is 2 and the traction speed is 5 m / min;

[0056] Step S5, Preliminary Cooling and Shaping: The blown film passes through the air cooling system. By arranging multiple cooling air rings around the film, cold air is blown onto the film surface to quickly cool down the film. The temperature of the cooling air is 10°C, so that the surface temperature of the release film is initially reduced to 80°C;

[0057] Step S6, Release Force Alienation Treatment: By setting gas spray guns on the upper and lower sides of the pulled film, nitrogen is sprayed on both sides of the film through the spray guns;

[0058] Among them, the spray gun pressure on the upper surface is 0.3 MPa, the gas flow rate is 30 L / min, and the treatment time is 30 s; the spray gun pressure on the lower surface is 0.2 MPa, the gas flow rate is 20 L / min, and the treatment time is 20 s;

[0059] Then, it is cooled again to naturally cool to room temperature. During the above treatment process, through the gas parameter treatment in the two-side treatment process, the change in the surface performance of the lower side is less than that of the upper side, so as to realize the adjustment and change of the release force on both sides of the release film to meet the actual needs;

[0060] Step S7, Reprocessing the Finished Product. During the processing, the release film is trimmed through a die-cutting device, and an easy-tear line is pressed on the die-cut and trimmed release film through a rotary indentation machine to facilitate subsequent actual use.

[0061] Example Two

[0062] A self-release release film, including raw materials with the following masses:

[0063] Base film: HDPE 40 g, LDPE 35 g, LLDPE 20 g, M-LDPE 10 g, CaCO 3 20 g, slip agent 1 g, anti-sticking agent 0.7 g, antistatic agent 2 g, antioxidant 0.6 g, ultraviolet absorber 0.6 g, plasticizer 12 g, flame retardant 14 g;

[0064] Release formulation: 10 g of perfluorooctylethyl acrylate, 6 g of trifluoroethyl methacrylate, 3 g of hydroxy-terminated polydimethylsiloxane, 2 g of curing agent, 0.01 g of initiator, 100 g of solvent.

[0065] Further, the slip agent is erucamide.

[0066] Further, the anti-sticking agent is talcum powder.

[0067] Further, the antistatic agent is sodium dodecyl sulfate.

[0068] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio of 1:2.

[0069] Further, the curing agent is an isocyanate curing agent.

[0070] Further, the solvent is a mixed solvent of fluorocarbon solvent and xylene with a volume ratio of 2:3.

[0071] A method for preparing a self-release release film includes the following steps:

[0072] Step S1, preparation of base film raw materials: Weigh the following raw materials according to parts by weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 - 15 min;

[0073] Step S2, preparation of release formulation solution: Perfluorooctylethyl acrylate, trifluoroethyl methacrylate, hydroxy-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0074] When preparing the release formulation;

[0075] First, add perfluorooctylethyl acrylate and trifluoroethyl methacrylate to the reaction kettle in proportion, and stir and mix at room temperature to obtain a fluorinated monomer mixture;

[0076] Then, slowly add hydroxy-terminated polydimethylsiloxane to the fluorinated monomer mixture and continue stirring to fully mix the two to form a single reaction system;

[0077] Polymerization reaction: Place the reaction kettle containing the above raw materials in a constant temperature water bath for heating, control the temperature at 70 °C, start the polymerization reaction, and then gradually add the initiator to initiate the polymerization reaction of the fluorinated monomer and siloxane. During the polymerization reaction, continuous stirring is required, and the reaction time is 6 h;

[0078] Cooling and discharging: After the polymerization reaction reaches the expected degree, stop heating, let the whole reaction system cool down to room temperature naturally, and take out the product. At room temperature, add the curing agent into the product to make the curing agent fully react with the hydroxyl group in the polymer to form a cross-linked structure, improve the performance of the subsequent coating, and add solvent to adjust the concentration of the polymer to prepare a fluorosilicone polymer solution as needed, so as to facilitate the subsequent coating process;

[0079] Step S3, fully mixing and stirring the release ingredient solution and the base film raw material to form a self-release release film raw material melt;

[0080] Step S4, extrusion blown film: adding the mixed base film raw material into the barrel of the extruder, and gradually heating, melting and plasticizing the raw material through the heating of the extruder and the rotation of the screw. The temperature in this process is maintained at 200° C. The plasticized melt is extruded through the die head to form a tubular film, and then compressed air is immediately introduced into the tube to blow the tubular film into a desired diameter and thickness. At the same time, the end of the film is pulled by a pulling device to ensure continuous production. In this process, the blowing ratio is 2.5 and the pulling speed is 10 m / min.

[0081] Step S5, preliminary cooling and shaping, the inflated film passes through an air cooling system, and by arranging multiple cooling air rings around the film, cold air is blown to the surface of the film to quickly cool the film. The temperature of the cooling air is 20°C, so that the surface temperature of the release film is initially reduced to 80°C;

[0082] Step S6, separation force differentiation treatment: by arranging gas spray guns on the upper and lower sides of the pulled film, nitrogen spraying treatment is performed on the upper and lower sides of the film through the spray guns;

[0083] The spray gun pressure on the upper surface is 0.3MPa, the gas flow rate is 30L / min, and the treatment time is 30s; the spray gun pressure on the lower surface is 0.2MPa, the gas flow rate is 20L / min, and the treatment time is 20s;

[0084] Then, the film is cooled again to naturally cool to room temperature. In the above treatment process, the gas parameters are processed during the treatment process on both sides so that the surface property change on the lower side is smaller than that on the upper side, thereby adjusting the release force on both sides of the release film to meet actual needs.

[0085] Step S7, reprocessing the finished product. During the processing, the release film is trimmed by a die-cutting device, and the easy-tear line of the release film after the die-cutting and trimming is pressed by a rotary creasing machine to facilitate subsequent practical use.

[0086] Embodiment 3

[0087] A self-release release film comprising the following qualities of raw materials:

[0088] Base film: HDPE 60g, LDPE 50g, LLDPE 30g, M-LDPE 20g, CaCO 3 30g, slip agent 2g, anti-sticking agent 1g, antistatic agent 3g, antioxidant 1g, ultraviolet absorber 1g, plasticizer 20g, flame retardant 20g;

[0089] Release formulation: perfluorooctylethyl acrylate 10g, trifluoroethyl methacrylate 6g, hydroxyl-terminated polydimethylsiloxane 3g, curing agent 2g, initiator 0.01g, solvent 100g..

[0090] Further, the slip agent is polydimethylsiloxane.

[0091] Further, the anti-sticking agent is polyethylene wax.

[0092] Further, the antistatic agent is lauryl alcohol polyoxyethylene ether.

[0093] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio, and the ratio of the two is 1:2.

[0094] Further, the curing agent is an isocyanate curing agent.

[0095] Further, the solvent is a mixed solvent of fluorocarbon solvent and xylene, and the volume ratio is 2:3.

[0096] A preparation method of a self-releasing release film includes the following steps:

[0097] Step S1, preparation of base film raw materials: Weigh the following raw materials according to parts by weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, plasticizer, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 - 15 minutes;

[0098] Step S2, preparation of release formulation solution: perfluorooctylethyl acrylate, trifluoroethyl methacrylate, hydroxyl-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0099] When preparing the release formulation;

[0100] First, add perfluorooctylethyl acrylate and trifluoroethyl methacrylate into the reaction kettle according to the ratio, and stir and mix at room temperature to obtain a fluorinated monomer mixture;

[0101] Subsequently, hydroxyl-terminated polydimethylsiloxane was slowly added to the fluorinated monomer mixture, and stirring was continued to fully mix the two to form a single reaction system;

[0102] Polymerization reaction: The reaction kettle containing the above raw materials was placed in a constant temperature water bath for heating, and the temperature was controlled at 80 °C to start the polymerization reaction. Then, an initiator was gradually added thereto to initiate the polymerization reaction of the fluorinated monomer and the siloxane. During the polymerization reaction, continuous stirring was required, and the reaction time was 8 h;

[0103] Cooling and discharging: After the polymerization reaction reached the expected degree, heating was stopped, and the overall reaction system was allowed to cool naturally to room temperature. Then the product was taken out. At room temperature, a curing agent was added to the product to allow the curing agent to fully react with the hydroxyl groups in the polymer to form a crosslinked structure, improving the performance of the subsequent coating. And as needed, a solvent was added to adjust the concentration of the polymer to make a fluorosilicon polymer solution, which was convenient for the subsequent coating process;

[0104] Step S3: The release formulation solution and the base film raw material were fully mixed and stirred to form a self-releasing release film raw material melt;

[0105] Step S4: Extrusion and blown film: The mixed base film raw material was added to the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw material was gradually heated and melted and plasticized. The temperature during this process was maintained at 250 °C. The plasticized melt was extruded through the die head to form a tubular film. Then, compressed air was immediately introduced into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the film was pulled by the traction device at the end to ensure continuous production. During this process, the blow-up ratio was 3 and the traction speed was 15 m / min;

[0106] Step S5: Preliminary cooling and shaping: The blown film passed through the air cooling system. By arranging a plurality of cooling air rings around the film and blowing cold air onto the film surface, the film was quickly cooled. The temperature of the cooling air was 10 °C - 30 °C, and the surface temperature of the release film was initially reduced to 80 °C;

[0107] Step S6: Release force dissimilation treatment: By arranging gas spray guns on the upper and lower sides of the pulled film, nitrogen gas was sprayed on the upper and lower sides of the film through the spray guns;

[0108] Among them, the spray gun pressure on the upper surface was 0.3 MPa, the gas flow rate was 30 L / min, and the treatment time was 30 s; the spray gun pressure on the lower surface was 0.2 MPa, the gas flow rate was 20 L / min, and the treatment time was 20 s;

[0109] Then, it is cooled again to naturally cool to room temperature. During the above treatment process, through the gas parameter treatment in the two-sided treatment process, the change in the surface performance of the lower side is less than that of the upper side, thereby realizing the adjustment and change of the release force on both sides of the release film to meet the actual needs;

[0110] Step S7: Reprocess the finished product. During the processing, trim the release film through a die-cutting device, and press the easy-tear line on the die-cut and trimmed release film through a rotary indentation machine to facilitate subsequent actual use.

[0111]

[0112]

[0113] In the above table:

[0114] The hardness of the formed release film is measured by a Shore hardness tester. And it can be known from reference to the above table that in the above embodiments, the mass ratio of CaCO 3 from large to small is Example 2, Example 3, and Example 1; and the hardness of the release film finished products in the three embodiments also follows the above rule from large to small. Therefore, it can be known that during the production of the release film, the mass ratio of CaCO 3 is positively correlated with the hardness of the release film;

[0115] It can also be known from the above table that the coefficient of thermal expansion of the release film finished product is negatively correlated with the addition amount of the plasticizer. The lower the mass ratio of the plasticizer in the total mass, the lower the coefficient of thermal expansion of the release film. On the contrary, the higher the proportion of the plasticizer in the total mass, the higher the coefficient of thermal expansion of the release film. Therefore, according to this rule, the release film can exhibit higher flexibility and molecular chain fluidity at lower temperatures and have a more obvious expansion when heated;

[0116] In the above table, the test method for the thickness deviation rate is as follows: Use a thickness measuring instrument to measure the thickness at different positions of the release film, calculate the thickness deviation. Under the condition that the process conditions are basically the same, the factor affecting the thickness deviation rate of the finished product is the traction speed of the finished product. It can be observed and measured from the finished products of Example 1 to Example 3 that the faster the traction rate of the finished product, the greater the thickness deviation rate of the finished product. Therefore, during the actual production process, it is necessary to select an appropriate traction rate for product traction to achieve the purpose of controlling the thickness deviation rate;

[0117] Comparative Example 1

[0118] A self-releasing release film, comprising raw materials with the following masses:

[0119] Base film: 30 g of HDPE, 20 g of LDPE, 10 g of LLDPE, 5 g of M-LDPE, CaCO 3 21 g, 0.3 g of slip agent, 0.3 g of anti-sticking agent, 1 g of antistatic agent, 0.3 g of antioxidant, 7 g of plasticizer;

[0120] Release formulation: 10 g of perfluorooctylethyl acrylate, 6 g of trifluoroethyl methacrylate, 3 g of hydroxyl-terminated polydimethylsiloxane, 2 g of curing agent, 0.01 g of initiator, 100 g of solvent.

[0121] Further, the slip agent is oleic acid amide.

[0122] Further, the anti-sticking agent is silicon dioxide.

[0123] Further, the antistatic agent is stearyl trimethyl ammonium chloride.

[0124] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio of 1:1.

[0125] Further, the curing agent is an isocyanate curing agent.

[0126] Further, the solvent is a mixed solvent of fluorocarbon solvent and xylene, with a volume ratio of 2:3.

[0127] A preparation method of a self-releasing release film includes the following steps:

[0128] Step S1, preparation of base film raw materials: Weigh the following raw materials according to parts by weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 minutes;

[0129] Step S2, preparation of release formulation solution: Perfluorooctylethyl acrylate, trifluoroethyl methacrylate, hydroxyl-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0130] When preparing the release formulation;

[0131] First, add perfluorooctylethyl acrylate and trifluoroethyl methacrylate to the reaction kettle in proportion, and stir and mix at room temperature to obtain a fluorine-containing monomer mixture;

[0132] Then, slowly add hydroxyl-terminated polydimethylsiloxane to the fluorine-containing monomer mixture, and continue stirring to make the two fully mixed to form a single reaction system;

[0133] Polymerization reaction: Place the reaction kettle containing the above raw materials in a constant temperature water bath for heating. Control the temperature at 60 °C and start the polymerization reaction. Then gradually add the initiator thereto to initiate the polymerization reaction of the fluorine-containing monomer and the siloxane. During the polymerization reaction, continuous stirring is required. The reaction time is 4 h;

[0134] Cooling and discharging: After the polymerization reaction reaches the expected degree, stop heating, let the overall reaction system cool down to room temperature naturally, and take out the product. At room temperature, add the curing agent to the product to make the curing agent react fully with the hydroxyl groups in the polymer to form a cross-linked structure, improve the performance of the subsequent coating, and add a solvent to adjust the concentration of the polymer to make a fluorosilicon polymer solution as needed to facilitate the subsequent coating process;

[0135] Step S3: Thoroughly mix and stir the release compounding solution and the base film raw materials to form a self-releasing release film raw material melt;

[0136] Step S4: Extrusion and blowing film: Add the mixed base film raw materials to the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw materials are gradually heated and melted and plasticized. The temperature during this process is maintained at 150 °C. The plasticized melt is extruded through the die head to form a tubular film. Then immediately introduce compressed air into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the end is pulled by the traction device to ensure continuous production. During this process, the blow-up ratio is 2 and the traction speed is 5 m / min;

[0137] Step S5: Preliminary cooling and shaping. The blown film passes through the air cooling system. By arranging multiple cooling air rings around the film and blowing cold air to the film surface, the film is quickly cooled. The temperature of the cooling air is 10 °C, so that the surface temperature of the release film is initially reduced to 80 °C;

[0138] Step S6: Release force differentiation treatment: Set gas spray guns on the upper and lower sides of the pulled film, and spray nitrogen on the upper and lower sides of the film through the spray guns;

[0139] Among them, the spray gun pressure on the upper surface is 0.3 MPa, the gas flow rate is 30 L / min, and the treatment time is 30 s; the spray gun pressure on the lower surface is 0.2 MPa, the gas flow rate is 20 L / min, and the treatment time is 20 s;

[0140] Then cool it again to make it cool down to room temperature naturally. During the above treatment process, through the gas parameter treatment in the two-sided treatment process, the change in the surface performance of the lower side is less than the change in the surface performance of the upper side, so as to realize the adjustment and change of the release force on both sides of the release film and meet the actual needs;

[0141] Step S7: Reprocess the finished product. During the processing, use a die-cutting device to trim the release film, and use a rotary indentation machine to press the tear lines on the die-cut and trimmed release film to facilitate subsequent actual use.

[0142] Comparative Example 2

[0143] A self-releasing release film, comprising raw materials with the following masses:

[0144] Base film: HDPE 30g, LDPE 20g, LLDPE 10g, M-LDPE 5g, CaCO 3 15g, slip agent 0.3g, anti-sticking agent 0.3g, antistatic agent 1g, antioxidant 0.3g, plasticizer 7g.

[0145] Further, the slip agent is oleic acid amide.

[0146] Further, the anti-sticking agent is silicon dioxide.

[0147] Further, the antistatic agent is stearyl trimethyl ammonium chloride.

[0148] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio, and the ratio of the two is 1:1.

[0149] A preparation method of a self-releasing release film, comprising the following steps:

[0150] Step S1: Preparation of base film raw materials: Weigh the following raw materials, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, plasticizer according to parts by weight, and put them into a high-speed mixer for thorough mixing. The mixing time is 5 - 15 min;

[0151] Step S4: Extrusion and blowing: Add the mixed base film raw materials into the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw materials are gradually heated and melted and plasticized. The temperature during this process is maintained at 150 °C. The plasticized melt is extruded through the die head to form a tubular film, and then compressed air is immediately introduced into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the end is pulled by a traction device to ensure continuous production. During this process, the blow-up ratio is 2 and the traction speed is 5 m / min;

[0152] Step S3: Cooling and shaping. The blown film passes through an air-cooling system. By arranging multiple cooling air rings around the film, cold air is blown onto the film surface to quickly cool the film to room temperature. The temperature of the cooling air is 10 °C;

[0153] Step S4: Reprocess the finished product. During the processing, use a die-cutting device to trim the release film, and use a rotary indentation machine to press tear lines on the die-cut and trimmed release film to facilitate subsequent actual use.

[0154] Comparative Example 3

[0155] A self-releasing release film, comprising raw materials with the following masses:

[0156] Base film: 30 g of HDPE, 20 g of LDPE, 10 g of LLDPE, 5 g of M-LDPE, CaCO 3 10 g, 0.5 g of slip agent, 0.3 g of anti-adhesive agent, 1 g of antistatic agent, 0.3 g of antioxidant, 7 g of plasticizer;

[0157] Release formulation: 10 g of perfluorooctylethyl acrylate, 6 g of trifluoroethyl methacrylate, 3 g of hydroxyl-terminated polydimethylsiloxane, 2 g of curing agent, 0.01 g of initiator, 100 g of solvent.

[0158] Further, the slip agent is oleic acid amide.

[0159] Further, the anti-adhesive agent is silica.

[0160] Further, the antistatic agent is stearyl trimethyl ammonium chloride.

[0161] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio, and the ratio of the two is 1:1.

[0162] Further, the curing agent is an isocyanate curing agent.

[0163] Further, the solvent is a mixed solvent of fluorocarbon solvent and xylene, and the volume ratio is 2:3.

[0164] A preparation method of a self-releasing release film, comprising the following steps:

[0165] Step S1: Preparation of base film raw materials: Weigh the following raw materials, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-adhesive agent, antistatic agent, antioxidant according to weight parts, and put them into a high-speed mixer for full mixing. The mixing time is 5 min;

[0166] Step S2: Preparation of release formulation solution: Perfluorooctylethyl acrylate, trifluoroethyl methacrylate, hydroxyl-terminated polydimethylsiloxane, curing agent, initiator, solvent;

[0167] When preparing the release formulation;

[0168] First, perfluorooctylethyl acrylate and trifluoroethyl methacrylate are added to the reaction kettle in proportion and stirred and mixed at room temperature to obtain a fluorinated monomer mixture;

[0169] Then, hydroxyl-terminated polydimethylsiloxane is slowly added to the fluorinated monomer mixture, and stirring is continued to fully mix the two to form a single reaction system;

[0170] Polymerization reaction: The reaction kettle containing the above raw materials is placed in a constant temperature water bath for heating, the temperature is controlled at 60 °C, and the polymerization reaction is started. Then, an initiator is gradually added thereto to initiate the polymerization reaction of the fluorinated monomer and the siloxane. During the polymerization reaction, continuous stirring is required, and the reaction time is 4 h;

[0171] Cooling and discharging: After the polymerization reaction reaches the expected degree, heating is stopped, and the overall reaction system is naturally cooled to room temperature. The product is taken out. At room temperature, a curing agent is added to the product to make the curing agent fully react with the hydroxyl groups in the polymer to form a cross-linked structure, improving the performance of the subsequent coating. And according to needs, a solvent is added to adjust the concentration of the polymer to make a fluorosilicone polymer solution, which is convenient for the subsequent coating process;

[0172] Step S3: The release compounding solution and the base film raw material are fully mixed and stirred to form a self-releasing release film raw material melt;

[0173] Step S4: Extrusion and blowing film: The mixed base film raw material is added to the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw material is gradually heated and melted and plasticized. The temperature during this process is maintained at 150 °C. The plasticized melt is extruded through the die head to form a tubular film. Then, compressed air is immediately introduced into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the film is pulled by a traction device at the end to ensure continuous production. During this process, the blow-up ratio is 2 and the traction speed is 5 m / min;

[0174] Step S5: Preliminary cooling and shaping. The blown film passes through an air-cooling system. By arranging multiple cooling air rings around the film, cold air is blown onto the film surface to quickly cool the film. The temperature of the cooling air is 10 °C, so that the surface temperature of the release film is initially reduced to 80 °C;

[0175] Step S6: Release force dissimilation treatment: By setting gas spray guns on the upper and lower sides of the pulled film, nitrogen gas is sprayed on the upper and lower sides of the film through the spray guns;

[0176] Among them, the spray gun pressure on the upper surface is 0.3 MPa, the gas flow rate is 30 L / min, and the treatment time is 30 s; the spray gun pressure on the lower surface is 0.2 MPa, the gas flow rate is 20 L / min, and the treatment time is 20 s;

[0177] Then, it is cooled again to naturally cool to room temperature. During the above treatment process, through the gas parameter treatment in the two-sided treatment process, the change in the surface performance of the lower side is less than that of the upper side, thereby realizing the adjustment and change of the release force on both sides of the release film to meet the actual needs;

[0178] Step S7: Reprocess the finished product. During the processing, trim the release film through a die-cutting device, and press an easy-tear line on the die-cut and trimmed release film through a rotary indentation machine to facilitate subsequent actual use.

[0179] Comparative Example 4

[0180] A self-releasing release film comprises raw materials with the following masses:

[0181] Base film: 30 g of HDPE, 20 g of LDPE, 10 g of LLDPE, 5 g of M-LDPE, CaCO 3 10 g, 0.4 g of slip agent, 0.3 g of anti-sticking agent, 1 g of antistatic agent, 0.3 g of antioxidant, 7 g of plasticizer.

[0182] Further, the slip agent is oleic acid amide.

[0183] Further, the anti-sticking agent is silicon dioxide.

[0184] Further, the antistatic agent is stearyl trimethyl ammonium chloride.

[0185] Further, the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a combined ratio of 1:1.

[0186] A preparation method of a self-releasing release film comprises the following steps:

[0187] Step S1: Preparation of base film raw materials: Weigh the following raw materials, HDPE, LDPE, LLDPE, M-LDPE, CaCO 3 , slip agent, anti-sticking agent, antistatic agent, antioxidant, plasticizer according to parts by weight, and put them into a high-speed mixer for full mixing. The mixing time is 5 - 15 min;

[0188] Step S4: Extrusion and blown film: Add the mixed base film raw materials into the barrel of the extruder. Through the heating of the extruder and the rotation of the screw, the raw materials are gradually heated and melted and plasticized. The temperature during this process is maintained at 150 °C. The plasticized melt is extruded through the die head to form a tubular film, and then compressed air is immediately introduced into the tube to blow up the tubular film to the required diameter and thickness. At the same time, the end is pulled by a traction device to ensure continuous production. During this process, the blow-up ratio is 2 and the traction speed is 5 m / min;

[0189] Step S3, cooling and shaping: The blown film passes through an air cooling system. By arranging multiple cooling air rings around the film, cold air is blown onto the film surface to quickly cool the film to room temperature. The temperature of the cooling air is 10°C.

[0190] Step S4, reprocessing the finished product. During the processing, the release film is trimmed by a die-cutting device, and a tear line is pressed on the die-cut and trimmed release film by a rotary indentation machine to facilitate subsequent actual use.

[0191]

[0192]

[0193] In the above table, the two items of contact angle (water) and contact angle (oil) indirectly evaluate the surface energy by the contact angle formed when the measuring liquid droplet is on the surface of the release film. When the liquid droplet contacts the solid surface, a certain contact angle will be formed. The larger the contact angle, the lower the surface energy of the solid surface and the smaller the interaction force with the liquid.

[0194] The measurement method of surface tension is to directly measure the surface tension of the release film using a surface tensiometer.

[0195] It can be seen from the above table that for Example 1, Comparative Example 1, and Comparative Example 3 using the release formulation, compared with Comparative Example 2 and Comparative Example 4 without using the release formulation, the surface of the produced release film product has a lower surface energy, has a better self-release effect, and the products using the release formulation have better waterproof and anti-oil pollution effects.

[0196] The detection method of the weight loss rate in an acidic environment is the percentage of the difference between the product quality obtained after soaking the finished product in a hydrochloric acid solution with pH = 2 for 72 hours and the original product quality. It is found from the above data that the products with the release formulation added have better corrosion resistance.

[0197] In the actual production process, when formulating the release formulation, an isocyanate curing agent is added, which plays a good role as a cross-linking agent, making the release layer form a cross-linked network structure. The cross-linked release layer has higher stability and cohesion, can effectively prevent the penetration and adsorption of viscous substances, and at the same time improve the heat resistance and chemical resistance of the release film, and better enhance the self-release performance of the product.

[0198] Moreover, it can be clearly seen from the above data that during the production process, after the raw materials doped with the release solution are subjected to release force differentiation treatment on the subsequent upper and lower surfaces, the corresponding release force parameters of the upper and lower sides of the produced release film can be effectively changed, and the release force parameters of the upper surface with larger treatment parameters and treatment time are significantly smaller than those of the lower surface with smaller treatment parameters and treatment time, thus realizing the differentiation of the release force on the upper and lower sides of the self-release release film produced, better meeting the actual use environment and facilitating normal use.

[0199] It can be known from the data of Example 1, Comparative Example 1 and Comparative Example 2 that:

[0200] When other parameters remain unchanged, the flatness of the release film is negatively correlated with CaCO 3 When the addition amount of CaCO 3 is larger, it is easy to cause the flatness of the release film not to be maintained, and the inflection point may occur when the mass of CaCO 3 accounts for about 20% of the total mass, as shown in the data of Comparative Example 1;

[0201] It can be known from the data of Example 1, Comparative Example 3 and Comparative Example 4 that:

[0202] When other parameters remain unchanged, the flatness of the release film is negatively correlated with the slip agent. When the addition amount of the slip agent is larger, it is easy to cause the flatness of the release film not to be maintained, and the inflection point may occur when the mass of the slip agent accounts for about 0.5% of the total mass, as shown in the data of Comparative Example 3.

[0203] In the actual production process of the present invention, the component ratio in the production process of the release film can be adjusted according to actual needs to realize the adjustment and control of the hardness, flatness, thermal expansion coefficient and thickness deviation rate of the finished release film, and it is convenient to produce a self-release release film that meets the requirements according to needs;

[0204] Moreover, in the production process, die-cutting and the pressing of the easy-tear line for the release film product can ensure the quality of the finished product and also facilitate the effective use of the subsequent product.

[0205] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A self-release release film, characterized in that: In parts by mass, it includes the following raw materials: Base film: HDPE 30-60 parts, LDPE 20-50 parts, LLDPE 10-30 parts, M-LDPE 5-20 parts, CaCO3 10-30 parts, lubricant 0.5-2 parts, anti-adhesive agent 0.3-1 parts, antistatic agent 1-3 parts, antioxidant 0.1-1 parts; Release ingredients: 10-15 parts of perfluorooctyl ethyl acrylate, 6-10 parts of trifluoroethyl methacrylate, 3-6 parts of terminal hydroxyl polydimethylsiloxane, 2-5 parts of curing agent, 0.01-0.1 parts of initiator, and 100-150 parts of solvent.

2. A self-release release film according to claim 1, characterized in that: The lubricant is any one of oleamide, erucamide or polydimethylsiloxane.

3. A self-release release film according to claim 1, characterized in that: The anti-sticking agent is any one of silicon dioxide, talcum powder and polyethylene wax.

4. The self-release release film according to claim 1, characterized in that: The antistatic agent is any one of stearyl trimethyl ammonium chloride, sodium lauryl sulfate, and lauryl alcohol polyoxyethylene ether.

5. The self-release release film according to claim 1, characterized in that: The antioxidant is a combination of antioxidant 1010 and antioxidant 168, and the ratio of the two is 1:1-1:

2.

6. The self-release release film according to claim 1, characterized in that: The curing agent is an isocyanate curing agent.

7. The self-release release film according to claim 1, characterized in that: The solvent is a mixed solvent of a fluorocarbon solvent and xylene, with a volume ratio of 2:

3.

8. A method for preparing the self-release release film according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step S1, preparation of base film raw materials: weigh the following raw materials according to weight, HDPE, LDPE, LLDPE, M-LDPE, CaCO3, lubricant, anti-adhesive agent, antistatic agent, antioxidant, and put them into a high-speed mixer for thorough mixing for 5-15 minutes; Step S2, preparing a release ingredient solution: perfluorooctyl ethyl acrylate, trifluoroethyl methacrylate, hydroxy-terminated polydimethylsiloxane, a curing agent, an initiator, and a solvent; When preparing the release ingredient solution; Firstly, perfluorooctyl ethyl acrylate and trifluoroethyl methacrylate are added into a reaction kettle in proportion, and stirred and mixed at room temperature to obtain a fluorine-containing monomer mixture; Then, the terminal hydroxyl polydimethylsiloxane is slowly added to the fluorine-containing monomer mixture, and stirring is continued to fully mix the two to form a single reaction system; Polymerization reaction: Place the reactor containing the above raw materials in a constant temperature water bath for heating, and control the temperature at 60°C-80°C to start the polymerization reaction, and then gradually add low-cost initiators to initiate the polymerization reaction of the fluorinated monomer and the siloxane. During the polymerization reaction, continuous stirring is required, and the reaction time is 4-8h; Cooling and discharging: After the polymerization reaction reaches the expected degree, stop heating, let the whole reaction system cool down to room temperature naturally, and take out the product. At room temperature, add the curing agent into the product to make the curing agent fully react with the hydroxyl group in the polymer to form a cross-linked structure, improve the performance of the subsequent coating, and add the solvent to adjust the concentration of the polymer to prepare a fluorosilicone polymer solution as needed, so as to facilitate the subsequent coating process; Step S3, fully mixing and stirring the release ingredient solution and the base film raw material to form a self-release release film raw material melt; Step S4, extrusion film blowing: adding the mixed raw material melt into the barrel of the extruder, and gradually heating, melting and plasticizing the raw material through the heating of the extruder and the rotation of the screw. The temperature in this process is maintained at 150°C-250°C. The plasticized melt is extruded through the die head to form a tubular film, and then compressed air is immediately introduced into the tube to blow the tubular film into a desired diameter and thickness. At the same time, the end of the film is pulled by a pulling device to ensure continuous production. In this process, the blowing ratio is 2-3 and the pulling speed is 5-15m / min; Step S5, preliminary cooling and shaping, the inflated film passes through an air cooling system, and by arranging multiple cooling air rings around the film, cold air is blown to the surface of the film to quickly cool the film. The temperature of the cooling air is 10°C-30°C, so that the surface temperature of the release film is initially reduced to 80°C; Step S6, release force differentiation treatment: by arranging gas spray guns on the upper and lower sides of the pulled film, nitrogen spraying treatment is performed on the upper and lower sides of the film through the spray guns; The spray gun pressure on the upper surface is 0.3MPa, the gas flow rate is 30L / min, and the treatment time is 30s; the spray gun pressure on the lower surface is 0.2MPa, the gas flow rate is 20L / min, and the treatment time is 20s; Then, the film is cooled again to naturally cool to room temperature. In the above treatment process, the gas parameters are processed during the treatment process on both sides so that the surface property change on the lower side is smaller than that on the upper side, thereby adjusting the release force on both sides of the release film to meet actual needs. Step S7, reprocessing the finished product. During the processing, the release film is trimmed by a die-cutting device, and the easy-tear line of the release film after the die-cutting and trimming is pressed by a rotary creasing machine to facilitate subsequent practical use.

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